A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure
Abstract [n]Cycloparaphenylenes ([n]CPPs, where n is the number of phenylene groups), consisting of 1,4-linked phenylene unit, have attracted much attention due to their cyclic π-conjugated structures and physical properties. However, functionalizing of the benzene rings of smaller [n]CPPs (n < 7...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-43907-7 |
| _version_ | 1797397869990248448 |
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| author | Naoki Narita Yusuke Kurita Kohtaro Osakada Tomohito Ide Hidetoshi Kawai Yoshitaka Tsuchido |
| author_facet | Naoki Narita Yusuke Kurita Kohtaro Osakada Tomohito Ide Hidetoshi Kawai Yoshitaka Tsuchido |
| author_sort | Naoki Narita |
| collection | DOAJ |
| description | Abstract [n]Cycloparaphenylenes ([n]CPPs, where n is the number of phenylene groups), consisting of 1,4-linked phenylene unit, have attracted much attention due to their cyclic π-conjugated structures and physical properties. However, functionalizing of the benzene rings of smaller [n]CPPs (n < 7) has been a challenge due to ring strain and steric hindrance of the substituents that hampers their synthesis. Here we show successful synthesis of a new [6]CPP derivative with twelve methoxy groups at the 2,5-positions of all benzene rings by utilizing our developed CPP synthesis method via a macrocyclic gold complex. This molecule exhibited a significantly higher oxidation potential caused by the electron-donating ability of the methoxy groups and the tubular molecular conformation, allowing facile oxidation to give dicationic species with in-plane aromaticity. Furthermore, this molecule successfully included with the guest molecules with a flexible alkyl chain in the cavity, enabling the creation of a CPP-based rotaxane, which exploited its mechanically interlocked molecular structure to the first experimental observation that the in-plane aromaticity in the center of the macrocycle. |
| first_indexed | 2024-03-09T01:16:28Z |
| format | Article |
| id | doaj.art-4be1798ac1da4c6d83d4551cdec89c66 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-09T01:16:28Z |
| publishDate | 2023-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-4be1798ac1da4c6d83d4551cdec89c662023-12-10T12:25:11ZengNature PortfolioNature Communications2041-17232023-12-0114111010.1038/s41467-023-43907-7A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structureNaoki Narita0Yusuke Kurita1Kohtaro Osakada2Tomohito Ide3Hidetoshi Kawai4Yoshitaka Tsuchido5Department of Chemistry, Faculty of Science, Tokyo University of ScienceDepartment of Chemistry, Faculty of Science, Tokyo University of ScienceLaboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of TechnologyDepartment of Chemical Science and Engineering, National Institute of Technology, Tokyo CollegeDepartment of Chemistry, Faculty of Science, Tokyo University of ScienceDepartment of Chemistry, Faculty of Science, Tokyo University of ScienceAbstract [n]Cycloparaphenylenes ([n]CPPs, where n is the number of phenylene groups), consisting of 1,4-linked phenylene unit, have attracted much attention due to their cyclic π-conjugated structures and physical properties. However, functionalizing of the benzene rings of smaller [n]CPPs (n < 7) has been a challenge due to ring strain and steric hindrance of the substituents that hampers their synthesis. Here we show successful synthesis of a new [6]CPP derivative with twelve methoxy groups at the 2,5-positions of all benzene rings by utilizing our developed CPP synthesis method via a macrocyclic gold complex. This molecule exhibited a significantly higher oxidation potential caused by the electron-donating ability of the methoxy groups and the tubular molecular conformation, allowing facile oxidation to give dicationic species with in-plane aromaticity. Furthermore, this molecule successfully included with the guest molecules with a flexible alkyl chain in the cavity, enabling the creation of a CPP-based rotaxane, which exploited its mechanically interlocked molecular structure to the first experimental observation that the in-plane aromaticity in the center of the macrocycle.https://doi.org/10.1038/s41467-023-43907-7 |
| spellingShingle | Naoki Narita Yusuke Kurita Kohtaro Osakada Tomohito Ide Hidetoshi Kawai Yoshitaka Tsuchido A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure Nature Communications |
| title | A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure |
| title_full | A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure |
| title_fullStr | A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure |
| title_full_unstemmed | A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure |
| title_short | A dodecamethoxy[6]cycloparaphenylene consisting entirely of hydroquinone ethers: unveiling in-plane aromaticity through a rotaxane structure |
| title_sort | dodecamethoxy 6 cycloparaphenylene consisting entirely of hydroquinone ethers unveiling in plane aromaticity through a rotaxane structure |
| url | https://doi.org/10.1038/s41467-023-43907-7 |
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